Electronic effects and mechanistic features in the rearrangement-displacement reactions of aryl(chloromethyl)diphenylsilanes with fluoride ion

✍ Scribed by Steve L Aprahamian; Harold Shechter

• Book ID: 104222001
• Publisher: Elsevier Science
• Year: 1990
• Tongue: French
• Weight: 321 KB
• Volume: 31
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)88733-x

✦ Synopsis

At 25OC aryl migrations from negatively-charged pentacoordinate silicon correlate with the abilities of the rearranging groups to bear negative charge, but at lower temperatures the migrations become less dependent on electron-withdrawing stabilization. Substituted (halomethyl)dimethylsilanes (1, Eq 1) react with hard or naked nucleophiles (F' and RO') to give products (3 and 4) of migration from silicon to carbon with loss of halide i0n.l The reactions are presumed to involve pentacoordinate silyl anions (2)ls2 whose subsequent rearrangement-displacements are largely controlled by the abilities of the migrating groups to bear negative charge.' Of concern, however, is that the migratory r: uiql-cy-x Nu' -X' CH I = ': -N"-Si-C%-R l Nu-Si-CH,-CH,